Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/59—Arsenic- or antimony-containing compounds

Definitions

• Antimony mercaptides have been proposed as stabilizers for vinyl halide resins to guard against degradation by heat during molding and working of the resin into useful articles.
• Prior art patents which disclose such antimony organic sulfur-containing compounds and their utility as stabilizers include U.S. Pat. Nos. 2,680,726; 2,684,956; 3,340,285; 3,399,220; 3,466,261 and 3,530,158.
• the antimony mercaptides have not been widely used as stabilizers because of various shortcomings including, for example, their propensity to exude from molded or worked PVC plastic stock, cost or lack of other advantages associated with their use which might outweigh such shortcomings.
• 3,887,508 is directed to improvements in the utilization of antimony organic sulfur-containing compounds in combination with metal carboxylates. As described in my U.S. Pat. No. 3,887,508, the utility and efficiency of such antimony compounds are improved in the heat stabilization of vinyl halide resins to an unexpected degree.
• the present invention is directed to further improvements in vinyl halide resin stabilizer systems of antimony organic sulfur-containing compounds.
• This invention in one of its aspects provides for synergistic heat stabilizer compositions of such antimony compounds as stabilizers and ortho-dihydric phenols. It has been found that early color heat performances of antimony organic sulfur-containing compounds are significantly improved according to the principles of this invention by their combination with ortho-dihydric phenols. Furthermore, improvements in long term heat stability are achievable along with early color heat improvements.
• antimony organic heat stabilizer compositions are provided which are liquids and shelf-stable at ambient temperatures. Such stable liquid compositions are easily formulated into vinyl halide resin systems and offer synergistically heat stabilized resin systems with enhanced resistance to both early discoloration and long term heat degradation of molded plastics.
• This invention is predicated in part upon the unexpected heat stabilization of vinyl halide resins by antimony organic sulfur-containing compounds in combination with certain phenols.
• a phenol selected from the group consisting of o-dihydric phenols and o-dihydric alkyl phenols, and mixtures thereof, and an antimony organic sulfur-containing compound together contribute highly unexpected heat stabilization to a vinyl halide resin. It has been found that synergistic heat stabilizations are provided by such compositions, i.e., the sum of the stabilizing effects of an amount of each component alone upon the resin is exceeded when the same amounts of components are together in the vinyl halide resin formula.
• Liquid antimony stabilizer compositions are also provided by this invention which remain stable during storage at ambient temperature.
• liquid antimony organic sulfur-containing compounds including antimony mercaptoacid esters, tend to deteriorate upon standing. Such deterioration is observed by the formation and/or precipitation of solids in the liquid compounds. The precise reasons for this deterioration phenomenon is unknown. Nevertheless, the resulting heterogeneous liquids not only increases the problems of measuring and mixing the antimony compounds into vinyl halide resins for stabilization, but practically speaking, heterogeneity causes a dissolute appearance which reduces the marketability of the antimony stabilizers.
• the liquid antimony stabilizers are also rendered shelf-stable at ambient temperatures by the incorporation of the ortho-dihydric phenolic component.
• the combination of components of this invention provides liquid shelf-stable compositions which heat stabilize vinyl halide resins in a very effective manner.
• Particularly useful stabilizer compositions of this invention are achieved with a total parts by weight range on the order of about 0.05 to about 5 parts by weight based upon 100 parts by weight (phr) of the vinyl halide resin.
• a most useful range of total parts by weight of stabilizer composition is on the order of about 0.05 to about 3 phr and this depends upon the desired heat stability in a particular vinyl halide resin composition consistent with other requirements and economies.
• the combination of o-dihydric phenol with the antimony organic sulfur-containing compound is utilized at total parts on the order of about 0.05 to about 3 phr; and where the o-dihydric phenol is from about 1 to about 10 percent by weight of the antimony compound.
• antimony organic sulfur-containing compounds which are of use in this invention are generally characterized as having the Sb-- S group or linkage.
• antimony organic compounds suitable for use in this invention are derived from trivalent antimony and include mercaptides which may be characterized by the following formula:
• R represents hydrocarbon or substituted hydrocarbon radicals such as those selected from the group consisting of alkyl, aryl or aralkyl.
• alkyls such as ethyl, propyl, butyl, octyl, nonyl, lauryl and octadecyl; aryls and aralkyls such as phenyl, benzyl, naphthyl, xylyl or phenyl ethyl and the like.
• the group SR of Formula I may be the rest of a mercaptan or mercapto alcohol. As indicated, aliphatic and aromatic mercaptans may be employed to form the group SR.
• aliphatic mercaptans those having 8 to 18 carbon atoms, e.g., decyl or dodecyl mercaptan are usually preferred because the lower mercaptans are unsuitable for the preparation and use of the stabilizers on account of their offensive smell.
• Suitable aromatic mercaptans are, for instance, thionaphthol, thiobenzyl alcohol, phenoxyethyl mercaptan, and others.
• suitable mercapto alcohols monothioethylene glycol, monothipropylene glycol, thioglycerol, thiodiethylene glycol, and others may be mentioned.
• antimony mercaptides are antimony trilaurylmercaptide, antimony triphenylmercaptide and antimony tribenzylmercaptide.
• Patents exemplifying this formula Sb(SR) 3 or a similar formula and a definition of compounds represented thereby include U.S. Pat. Nos. 2,684,956 and 3,466,261, among others.
• Antimony organic sulfur-containing compounds other than the antimony mercaptides of the Formula I above are suitable for use according to this invention. Such compounds are generally termed antimony mercaptoacid esters which may be further defined by the following formula:
• R is selected from the group consisting of alkylene, arylene, and aralkylene radicals and R' is a substituted or unsubstituted alkyl, aryl or mixed aryl-alkyl group.
• R may be derived from mercapto acetic, ⁇ -mercaptopropionic, thiomalic, thiosalicyclic acids, etc.
• R' may be derived from decanols, glycerol, glycol, monoesters, dihydroabietyl alcohol, phenoxyethanol, pentaerythritol, etc.
• esters of mercapto alcohols such as thioglycols, in which the hydroxy groups are esterified by an aliphatic, aromatic or alicyclic saturated or unsaturated monocarboxylic acid.
• mercaptoacid esters are the esters of thioglycolic acid, such as ethyl thioglycolate, isooctylthioglycolate, and generally the esters of mono and dibasic aliphatic and aromatic mercapto acids, such as esters of beta thiopropionic acid, thiolactic acid, thiobutyric acid and mercapto lauric acid.
• antimony mercaptoacld esters include antimony tris (isooctylthioglycolate), antimony tris (glycoldimercaptoacetate), antimony tris (dodecylthioglycolate), dodecylmercaptoantimony bis(isooctylthioglycolate), and antimony tris (isoctyl- ⁇ -mercaptopropionate).
• Patents exemplifying Formula II or a similar formula and a definition of compounds represented thereby include U.S Pat. Nos. 2,680,726 and 3,530,158, among others.
• R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, and mixed aryl-alkyl, and substituted groups thereof, where X is selected from the group consisting of sulfide (sulfur) or mercaptide and n is an integer of 0 to 2.
• X groups are SR and SRCOOR' defined by Formulas I and II above wherein R of the group SR is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof, where R of the group SRCOOR' is selected from alkylene, arylene, aralkylene, and substituted groups thereof, wherein R' of the group SRCOOR' is selected from alkyl, aryl, mixed aryl-alkyl, and substituted groups thereof.
• R of the group SRCOOR' is selected from alkylene, arylene, aralkylene, and substituted groups thereof.
• the compound may be RSbX as exemplified hereinafter by n-butyl antimony sulfide where n of R n in Formula III is 1 and where n of X 3-n is 2. It is therefore appreciated that the formulas herein are merely representative indicia of the class of antimony compounds which respond to the teachings of this invention.
• R n SbX 3-n which may be used in practice of this invention, R may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or aryl including such groups when inertly substituted.
• R When R is alkyl, it may include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, n-octyl, 2-ethylhexyl, etc. as well as substituted alkyls including phenylethyl, benzyl, etc.
• Typical alkenyl groups which may be employed may include vinyl, 2-propenyl (i.e. allyl), 1-propenyl, 1-butenyl, 2-butenyl, etc. as well as inertly substituted alkenyl groups typified by 4-phenyl, buten-1-yl, etc.
• Typical cycloalkyl groups may include cyclohexyl, cycloheptyl, cyclooctyl as well as inertly substituted cycloalkyl groups including 2-methyl cycloheptyl, 3-butyl cyclohexyl, 3-methylcyclohexyl, etc.
• Typical alkynyl groups which may be employed include propyn-1-yl, propyn-2-yl, butyn-1-yl, phenlethynyl, ethynyl, etc.
• Typical aryl groups which may be employed may include phenyl, tolyl, xylyl, chlorophenyl, dimethylaminophenyl, etc.
• Typical mercaptides include phenyl mercaptide, lauryl mercaptide, butyl mercaptide, or dimercaptides including aliphatic, cycloaliphatic, or aromatic dimercaptans of the R groups disclosed herein, etc.
• n is 1 to 2
• Specific compounds when n is 1 to 2 include n-butyl antimony dilaurylmercaptide, n-butyl antimony sulfide, di-n-butyl antimony lauryl mercaptide, diphenyl antimony lauryl mercaptide, ditolyl antimony n-amyl mercaptide, dibenzyl antimony benzyl mercaptide, diallyl antimony cyclohexyl mercaptide, diphenyl antimony allylmercaptide, dicyclohexyl antimony n-hexyl mercaptide, ditolyl antimony phenyl mercaptide, di-isopropyl antimony 2-ethylhexyl mercaptide, di-p-chlorophenyl antimony n-butyl mercaptide, diphenyl antimony ethyl mercaptoacetate.
• Patents exemplifying such antimony compounds include U.S. Pat. Nos. 3,530,158 and 3,399,220.
• the R group is aryloxy, alkyloxy, alkaryloxy, acyloxy, etc.
• specific examples from which this group is derived may include 2-ethylhexanol, phenol, nonylphenol, xylenol, 2-ethylhexoic acid, oleic acid, lauric acid, benzoic acid and the like.
• phenol and phenols as used herein are intended to include mono- or polynuclear phenols exemplified by the benzene or naphthalene nucleus, and, the alkyl substituted forms of such nucleus.
• the ortho-dihydric phenols of such mono or polynuclear phenols have been found to provide synergistic stabilizing effectiveness with the antimony organic sulfur-containing compounds. These phenols additionally have been found to provide liquid, shelf-stable compositions of antimony compounds at ambient temperatures.
• Specific examples of such ortho-dihydric phenols which have presently been found advantageous are catechol, tertiary butyl catechol and 2,3 dihydroxynaphthalene.
• phenols may be represented by the following structural formula which also characterizes the ortho-dihydroxy phenols according to the broader aspects of this invention: ##STR1## where R 1 , R 2 , R 3 or R 4 is either hydrogen, alkyl, or may be a carbon residue which forms a part of an aromatic or alkylated aromatic nucleus as is the case when the phenolic nucleus is naphthalene.
• Alkyl substituted groups of mono or polynuclear phenols of this formula include straight or branched chain groups of C 1 -12 , such as methyl, ethyl, propyl, pentyl, hexyl, heptyl, dodecyl, or tertiary butyl, isopropyl, etc., forms.
• the presently most preferred phenols of this invention are the catechol derivatives because of their best performance and commercial availability.
• Other monohydric or trihydric phenols, or other functionally substituted mono-, di- or trihydric phenols have not been presently found to provide synergistic resin heat stabilizing activities.
• a standard resin formula which contained 200 parts by weight of polyvinyl chloride homopolymer which is characterized as a white powder having a particle size such that 100% passes through a 42 mesh screen at a specific gravity of 1.40 (Geon 103 EP by B. F. Goodrich). Included in the standard resin formula is also 6 parts by weight of a processing aid which is an acrylic polymer in powdered form which improves the hot processing of rigid and plasticized vinyl compounds (Acryloid K120N by Rohm and Haas Company). This material is a fine, white free flowing powder having a bulk density at about 0.30 grams per cc and a viscosity, 10% toluene, at 600 cps (Brookfield).
• the processing aid merely facilitates hot processing and forms no part of this invention.
• Calcium stearate was also employed at 2 parts by weight in the resin formula.
• standard resin blank or just “blank” is used hereinafter in these examples to designate the standard resin formula without heat stabilizer additives.
• Various combinations of the antimony organic sulfur-containing compounds and phenols were first blended together to form a shelf-stable liquid or solid phase composition and then mixed into the standard resin formula according to the following examples on a parts by weight basis. All amounts of such stabilizer components, in the tables and examples, are on a parts per hundred resin basis, or as indicated above, simply "phr". The phenols were incorporated in the stabilizer composition on the basis of about 5 percent by weight of the antimony compound.
• the long term heat stability contributions of the stabilizer compositions (or components thereof) hereinafter are determined by ascertaining the number of minutes at the test temperature required for the samples to degrade by severe darkening to a dark red or black.
• the term long term "heat stability contribution” is used to indicate the amount of heat stability in minutes contributed by a composition or component to the resin blank formula. Early color performances of the examples were observed as the term was defined above.
• Table I demonstrates that at 0.05 phr of each of the o-dihydric phenols alone, stability of the blank was not improved. In contrast, the ATP alone at about 0.95 phr contributed about 40 minutes of heat stabilizing effectiveness to the blank. Therefore, in general the o-dihydric phenol component of the stabilizer combination does not contribute to the long term heat stability of the blank formula; whereas, ATP contributed to such long term heat stability of the blank.
• Example 2 of Table I in which 0.05 part of 4-tertiary butyl catechol alone did not contribute heat stability to the blank.
• 0.95 part of ATP contributed about 40 minutes of heat stability to the blank.
• the expected heat stability of a combination of 0.05 phr of the t-butyl catechol and 0.95 ATP should have been about 40 minutes or less.
• the heat stability of such a combination was 60 minutes and heat stability synergism thus was clearly demonstrated.
• the same synergistic comparisons are made for the combinations of ATP with catechol or 2,3-dihydroxynaphthalene with reference to Examples 1 and 4-7.
• Example 1 which contained ATP alone had already started to yellow, and this yellowing worsened until, after 40 minutes, the test sample turned dark orange.
• Examples 3, 5 and 7 which contained the combination of ATP with each o-dihydric phenol, the samples remained essentially colorless during milling and until after about 15 minutes of oven testing. Only after about 20 minutes of oven treatment at 375° F. did the test samples of Examples 3, 5 and 7 start to turn a slight yellow, but even then, not to a degree of yellow exhibited by the ATP Example 1 upon even milling.
• These examples demonstrate the surprising heat stabilizing effectiveness of the o-dihydric phenol in the combination with an antimony organic sulfur-containing compound to resist early discoloration of vinyl halide resin formulations.
• antimony organic sulfur-containing compounds and o-dihydric phenols.
• Examples 8-11 were performed.
• antimony tris (laurylmercaptide) was substituted for the antimony tris (isooctylmercaptopropionate) and antimony tris (laurylmercaptide) is designated hereinafter as "ATL".
• ATL is a pasty solid at ambient temperatures and the phenolic components were blended therewith prior to the addition of the combination of components to the resin formulas. Because the phenolic component is added generally in a minor amount, it is preferred for good blending to first combine it with the antimony compound rather than add it separately to the resin formula.
• Example 8 which contained ATL alone had already yellowed and the yellowing worsened until, after 40 minutes, the test sample turned dark orange.
• Examples 9-11 which contained the combination of ATL with each o-dihydric phenol, the samples remained essentially colorless during milling and until after about 15 minutes of oven testing. Only after about 20 minutes of oven treatment at 375° F. did the test samples 9-11 start to turn a slight yellow, but even then, not to a degree of yellow exhibited by the ATL alone in Example 8 upon even milling.
• a standard resin formula which contained 200 parts by weight of polyvinyl chloride homopolymer (Diamond 450 by Diamond Shamrock). Included in the standard resin formula is also 6 parts by weight of a processing aid which, as stated above, is an acrylic polymer in powdered form which improves the hot processing of rigid and plasticized vinyl compounds. (Acryloid K120N by Rohm and Haas Company). A paraffin wax lubricant, i.e., a commercial wax designated 165 (H. M. Royal, Inc.) was also employed at 0.5 parts by weight in the resin formula. In addition, the resin formula contained 2 parts by weight of calcium stearate and 2 parts by weight of TiO 2 as a white pigment.
• standard resin blank or just “blank” is used hereinafter in these examples to designate the standard resin formula without heat stabilizer additives.
• Various combinations of the liquid antimony tris (isooctylthioglycolate) i.e. "ATG”, and phenols were first blended to form shelf-stable homogeneous liquids containing about 5% by weight of the phenol in the combination.
• TCG liquid antimony tris
• C means catechol
• DHN means 2,3-dihydroxynaphthalene.
• the stabilizer combinations were mixed into the standard resin formula according to the following examples on the parts by weight basis.
• Examples 12-27 clearly demonstrate that the ATG or antimony tris (isooctylthioglycolate) in combination with either o-dihydric phenol improves the early color performance of the ATG alone.
• the total whiteness ratings of each of the combinations versus the whiteness rating of the ATG alone is indicative of far superior performance of the combinations.
• antimony organic compounds display synergisms with o-dihydric phenols.
• Dodecylmercaptoantimony bis (isooctylthioglycolate), antimony tris (glycoldimercaptoacetate), or antimony tris (dodecylthioglycolate) are substituted for the antimony organic sulfur-containing compounds of the preceding examples and employing similar procedures, similar synergistic heat stabilizing performances with o-dihydric phenols are demonstrated.
• the metal carboxylate i.e., calcium stearate was employed and it is especially preferred to include such carboxylates in the stabilizer composition of this invention to achieve the advantageous stabilizing effectiveness as fully developed in my issued U.S. Pat. No. 3,887,508, and such disclosure is incorporated herein by reference.
• the metal carboxylate is an alkali or alkaline earth metal salt of a carboxylic or thiocarboxylic acid.
• the most useful metal salts of organic acids are those with lubricating characteristics such as the metal salts of fatty acids, more particularly, about C 8 -C 24 mono- carboxylic acids such as lauric and stearic acids; saponified synthetic fatty acids of about C 24 -C 54 such as C 36 or C 54 dimer and trimer acids; and partially saponified ester waxes such as Hoechst Wax OP which is an ester of montan wax partially saponified with lime, e.g., C 28 -C 32 carboxylic acids which are partially esterified with a dihydric alcohol and then saponified with lime to produce partially saponified ester waxes.
• the metal salts of fatty acids more particularly, about C 8 -C 24 mono- carboxylic acids such as lauric and stearic acids; saponified synthetic fatty acids of about C 24 -C 54 such as C 36 or C 54 dimer and trimer acids; and partially saponified ester waxes such as Hoechst Wax
• nonlubricating carboxylates such as acetates, benzoates or 2-ethyl hexoates are suitable.
• alkali or alkaline metal carboxylates include sodium stearate, lithium stearate, calcium stearate, calcium laurate, barium laurate, barium stearate, magnesium stearate, and strontium stearate.
• the vinyl halide resin which was employed is a homopolymer of vinyl chloride, i.e., polyvinyl chloride. It is to be understood, however, that this invention is not limited to a particular vinyl halide resin such as polyvinyl chloride.
• Other halogen-containing resins which are employed and illustrate the principles of this invention include chlorinate polyethylene, chlorinated polyvinyl chloride and the vinyl halide resin type.
• Vinyl halide resin as understood herein, and as appreciated in the art, is a common term and is adopted to define those resins or polymers usually derived by polymerization or copolymerization of vinyl monomers including vinyl chloride with or without other comonomers such as ethylene, propylene, vinyl acetate, vinyl ethers, vinylidene chloride, methacrylate, styrene, etc.
• a simple case is the conversion of vinyl chloride H 2 C ⁇ CHCl to polyvinyl chloride (CH 2 --CHCl--) n wherein the halogen is bonded to the carbon atoms of the carbon chain of the polymer.
• vinyl halide resins examples include vinylidene chloride polymers, vinyl chloride-vinyl ester copolymers, vinyl chloride-vinyl ether copolymers, vinyl chloride-vinylidene copolymers, vinyl chloride-propylene copolymers; and the like.
• vinyl halide commonly used in the industry is the chloride, although others such as bromide and fluoride may be used. Examples of the latter polymers include polyvinyl bromide, polyvinyl fluoride, and copolymers thereof.

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• 1975
  • 1975-06-30 US US05/592,038 patent/US4029618A/en not_active Expired - Lifetime
• 1976
  • 1976-04-12 CA CA250,090A patent/CA1084690A/fr not_active Expired
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• 1977
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